EP2200813A2 - Materialsystem und verfahren zum verändern von eigenschaften eines kunststoffbauteiles - Google Patents
Materialsystem und verfahren zum verändern von eigenschaften eines kunststoffbauteilesInfo
- Publication number
- EP2200813A2 EP2200813A2 EP08801346A EP08801346A EP2200813A2 EP 2200813 A2 EP2200813 A2 EP 2200813A2 EP 08801346 A EP08801346 A EP 08801346A EP 08801346 A EP08801346 A EP 08801346A EP 2200813 A2 EP2200813 A2 EP 2200813A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- medium
- component
- plastic component
- material system
- plastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000004033 plastic Substances 0.000 title claims abstract description 47
- 229920003023 plastic Polymers 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims description 42
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 230000008595 infiltration Effects 0.000 claims description 22
- 238000001764 infiltration Methods 0.000 claims description 22
- 230000005855 radiation Effects 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 13
- 239000002344 surface layer Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 11
- 238000007639 printing Methods 0.000 claims description 5
- 230000000051 modifying effect Effects 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- FMTLDVACNZDTQL-UHFFFAOYSA-N 5-ethyl-1,3-diazinane-2,4,6-trione Chemical compound CCC1C(=O)NC(=O)NC1=O FMTLDVACNZDTQL-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- AOIDYWIUVADOPM-UHFFFAOYSA-N 2-hydroxyethyl 2,3-dimethylbut-2-enoate Chemical compound CC(C)=C(C)C(=O)OCCO AOIDYWIUVADOPM-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000110 selective laser sintering Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000037338 UVA radiation Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
- B05C3/005—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material incorporating means for heating or cooling the liquid or other fluent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
- B05C3/02—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material the work being immersed in the liquid or other fluent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0283—Flat jet coaters, i.e. apparatus in which the liquid or other fluent material is projected from the outlet as a cohesive flat jet in direction of the work
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Definitions
- the invention relates to a material system and a method for changing the properties of a plastic component.
- a thin layer of powdered component is applied to a build platform. Subsequently, a portion of the powder is selectively bound, for example by applying binder. This selection corresponds to a section through the component to be achieved.
- the construction platform is lowered by one layer thickness and provided with a new layer of particulate material, which is also solidified as described above. These steps are repeated until a certain desired height of the object is reached.
- the printed and solidified areas create a three-dimensional object.
- Such a method is known for example from DE 69634921.
- other powder-based rapid prototyping processes such as electron beam sintering, in which each a loose particulate material also applied in layers and selectively solidified using a controlled physical radiation source work in a similar manner.
- the components produced by means of generative 3D processes often have a certain porosity.
- the porosity of the components is mostly due to the method of selective bonding.
- the connection by a laser beam corresponds to the well-known sintering.
- the grains of the powder combine at their points of contact by melting together.
- the space between the grains remains free.
- the situation is similar in the case of components in which the selective hardening is achieved by metering in a liquid (SD printing). If the smallest possible amount of liquid is metered in compared to the powder mass per unit of space, a porous body is formed. This is known, for example, from DE 60008778.
- the absorbency of porous parts makes it possible, similar to the known method for the production of fiber composites, to introduce liquid media into the component.
- DE 195 45 167 A1 discloses coating a model produced by selective laser sintering with wax so that a closed surface is formed. subsequent Immersion processes in liquid molding material require a liquid-tight part to ensure the dimensional accuracy of the mold. The strength properties are in the background here. The process uses the thermal phase transition from solid to liquid and vice versa.
- a disadvantage of a generalization of this procedure is that, depending on the infiltration material, the component must be exposed to considerable temperatures.
- infiltration materials with a low melting point usually also have low strength values.
- infiltration resins which are introduced liquid into the porous body and solidify in the form of dispersions with evaporation of the solvent or as resin mixtures by a polymerization in the component.
- Such processes are known, for example, from WO 2005/82603 A1, US Pat. No. 6,375,874 and US Pat. No. 5,616,294.
- Such dispersions described in these documents are suitable only for thin-walled components due to the need to evaporate the solvent.
- Thermal processes based on the model of wax infiltration are not very suitable for increasing the strength due to the temperature sensitivity for porous plastic components.
- Polymerizing mixtures for infiltration are usually 2-component systems, such as epoxy resins. Such mixtures achieve high strength values. To the properties however, they are not sufficient for industrially polymerized products, such as PE, PET, PMMA.
- Polymerizing mixtures as known in the art, have the following limits.
- the polymerizing infiltrate forms with the porous component or the matrix a composite material which is weakened by the phase boundaries in the interior.
- the strength values of the components are therefore always below the values of the pure infiltrate.
- a binder component and a resin component are mixed together prior to introduction into the component.
- the polymerization then starts with a time delay.
- a disadvantage of this method is that a once set mixture must be processed within a short period of time.
- An immersion method that enables high quantities and a high degree of automation can not be realized economically. The job is usually done by painting with a brush. This method can not be automated and is a complex task for complex geometries.
- This object is achieved by a method for modifying properties of a plastic component, in which medium is introduced into the plastic component having a porosity and the medium makes a homogeneous connection with it by at least partially releasing the plastic component. Furthermore, the object is achieved by a material system comprising a medium for introduction into a plastic component having a porosity, in which the medium has at least one substance which at least partially dissolves the plastic component and forms a homogeneous connection therewith.
- the properties of the components can be specifically improved.
- the creation of porous components, which are subsequently infiltrated is much less time-consuming than the creation of components with very high fluid input, which is necessary to directly create dense parts in the generative process.
- materials are now used for infiltration, which can dissolve the generatively produced matrix and thus lead to a particularly homogeneous material. dissolve means, therefore, that a homogeneous connection between the matrix and the medium, in particular infiltrate arises.
- the solidification of the introduced medium takes place by polymerization.
- an edge layer of the plastic component is accelerated accelerated by chemical and / or physical measures compared to the other plastic component.
- the component is accelerated in the peripheral layer, in contrast to the rest of the component volume, accelerated and produced in this way a stable framework.
- the softening by the dissolution of the matrix can thus not influence the geometry.
- the surface layer solidification could, for example, be carried out by additional application of accelerators and the use of polymerization media with radiation initiation.
- Accelerated could be defined in such a way that solidification of an edge layer takes place noticeably faster than solidification of the rest of the body. And solidification is not to understand that a complete consolidation has taken place.
- a dimensional stability that is to say a stability bearing the dead weight, is often sufficient.
- the faster solidification of the surface layer could be done in accordance with an embodiment of the present invention by the use of two Polymerisationssyteme with different reaction times.
- the faster solidification of the surface layer is achieved by the entry of high-energy radiation, such as UV radiation or microwave radiation.
- Another embodiment of the method according to the invention represents the possibility of introducing the medium into the plastic component by means of immersion in a bath of the medium.
- the porous component could now be automatically infiltrated in a dipping bath.
- the immersion bath itself does not harden, so that a lasting and economical use of the immersion bath is guaranteed.
- the liquids of the immersion bath give high strength properties after the polymerization.
- the material of the porous component makes a connection with the infiltrate, which is similar to a homogeneous material.
- the curing of the resin should be carried out in an advantageous manner in the time range of a few minutes.
- the plastic component can further be immersed in a bath with an accelerator. Furthermore, according to the present invention, it may be advantageous if the component is rotated at least during the introduction of medium and / or high-energy radiation.
- This rotation could be done by one or more axes.
- a turntable with one or more degrees of freedom could be provided for moving the component.
- the component In order to ensure the access of the radiation when using the radiation curing, the component is held in as little as possible shielding the radiation holder, for example wires.
- a simple embodiment is a grate, which is connected to a rotation axis.
- a material system according to the present invention comprises a medium for introduction into a porosity-having plastic component.
- the medium has at least one substance which at least partially dissolves the plastic component and forms a homogeneous connection with it.
- the medium is a monomer.
- the medium has at least one constituent which is of the same class of substance as a plastic constituent of the plastic component.
- the material in the medium preferably contains a monomer which is also a constituent of the bridges or the grains of the matrix, ie of the plastic component, or a foreign monomer which dissolves the generatively produced body. Due to the resolution by the liquid solidifies the generatively produced body in a homogeneous manner.
- the material system further comprises a catalyst and / or a crosslinker.
- a photoinitiator is also provided.
- the photoinitiator is provided in the medium.
- the plastic component and the medium have a methacrylate.
- Both the material system according to the invention and the method according to the invention can preferably be used for infiltrating porous plastic components, in particular plastic components produced by means of 3-D printing methods.
- FIG. 1 shows an uninfiltrated and an infiltrated matrix
- Figure 2 illustrates an infiltrated matrix according to one embodiment of a method and material system of the present invention
- Figure 3 is a surface hardening according to a preferred embodiment of the present invention.
- Figure 4 is a dip according to a preferred embodiment of the present invention.
- Figure 5 is a dip according to another preferred embodiment of the present invention.
- FIG. 6 shows the irradiation of the component according to a preferred embodiment of the present invention and a spray application method for liquid application according to a preferred embodiment of the present invention
- Figure 7 shows a holder according to a preferred embodiment of the present invention.
- a medium 5 is to be introduced into a plastic component 10.
- the basis for this is a porous component 10.
- a porous component 10 or the matrix 4 is formed by grains 1 and connecting bridges 2, and between the grains 1 are the cavities 3 or pores of the matrix 4.
- the present invention relates to bodies whose grains are made of plastic.
- the bridges 2 of the matrix 4 may consist of a material similar or similar to the grains 1.
- the connecting bridges 2 between the grains 1 can be produced during the formation of the plastic component 10 or matrix 4 by means of various methods.
- the bridges 2 are formed from molten material which is produced by the action of heat by the laser beam. This means that the bridges 2 are formed from the material of the grains 1.
- porous plastic components are used, in which the bridges 2 and the material of the grains 1 belong to a chemically similar plastic system.
- the temperature control in the laser sintering process and the metered amount of the binder material in 3D printing, the porosity of the component can be controlled within certain limits.
- a liquid medium which corresponds in its chemical composition to the material system of grains 1 and 2 bridges.
- the medium 5 penetrates into the cavities 3 by capillary action.
- the solidification of the medium or infiltrate 5 forms a dense body. Excess material 5 drips off from the surface 6 of the component 10 and, after solidification, the plastic component has a smoother surface than in the uninfiltrated state.
- FIG. 2 shows that, in accordance with the present invention, in order to achieve high strengths, it has proved advantageous if the medium 5 has a dissolving force with respect to the matrix 4, which should preferably not be insignificant. As part of such a medium 5, it is possible to dissolve the grains 1 and bridges 2 7 and thereby form a homogeneous bond during solidification.
- the medium comprises 5 monomers which, if appropriate with the addition of auxiliaries, become solidified in or with the component 10 by the formation of molecular chains / structures.
- the polymerization can take place by the reaction types polyaddition, polycondensation, free-radical and ionic polymerization or ring-opening polymerization.
- homopolymers, as a chain of a monomer, or copolymers can be used by the polymerization of different monomers.
- the monomers used preferably have a low viscosity.
- the medium 5 in addition to various monomers, further constituents.
- initiators initiating the reaction accelerating catalysts and strength-increasing, crosslinking constituents can be added to the medium 5.
- These substances can also be used to control the reaction process.
- reaction inhibiting substances inhibitors may be included.
- the components necessary for the formation of a polymerizing substance can be introduced in separate phases of the production of the workpiece. Initiating components or catalysts may be incorporated in the powder or grains 1 or bridges 2 of the component 10 during the generative build process. These components can either perform a chemical function during the building process and during infiltration, or two separate systems are realized.
- a matrix solution is carried out in the method according to the invention and a stabilization of the surface layer 8 of the component 10 is produced.
- This is preferably achieved by means of two polymerization systems which react with a time delay.
- the fast system produces a thin, firm edge layer 8 in preferably a few seconds.
- the second reaction which solidifies the bulk or "inner" part of the material volume 9 (main reaction), takes place in a larger time frame.
- an initiating system which is bound in the powdery material or is present on its surface, that is to say during the generative production of the component.
- This system can for example start a radical polymerization.
- the powdery material constituting the porous member is made of polymethyl methacrylate (PMMA) or Polyethy ⁇ metacrylat (PEMA) consists.
- the grain contains the initiator dibenzoyl peroxide (BPO).
- BPO can be made accessible to the reaction via the dissolution action of the monomer in the infiltration fluid.
- the medium 5 is missing in the preferred method, a necessary for a self-curing component (initiator or catalyst / accelerator).
- the infiltrate 5 thus cures only in contact with the component 10. This allows it to be kept in a bath for automated dipping infiltration.
- Preferred for infiltration is a mixture of a monomer or a monomer mixture and a catalyst.
- a crosslinker may be added.
- Low viscosity monomers are particularly suitable here. Together with the initiator in the component results in a polymerizable mixture.
- HEMA 2-hydroxyethyl methacrylate
- DMPT N, N-dimethyl-p-toluidine
- Crosslinkers are added to control the heat of reaction in the main consolidation.
- ethylene glycol dimethyl methacrylate ELDMA
- HEMA ethylene glycol dimethyl methacrylate
- CuAA copper acetyl acetonate
- a liquid component can be used. This may contain an initiator or catalyst in a large amount, compared to the actual infiltration mixture.
- the infiltration mixture can be admixed with a component which can be activated by radiation.
- a component can be present in gaseous form and thus come into uniform contact with all edges of the component.
- the use of a liquid component takes place in an additional immersion step, which is followed by the actual infiltration.
- the additional liquid may use a catalyst or initiator.
- the catalyst DMPT is immersed in a grain having BPO and / or CuAA in an ethyl barbituric acid system in which the component is immersed. Due to the low diffusion in the component, only one surface layer is solidified during this procedure.
- the wetting of the surface layer 8 may be carried out as shown in FIG. 6, rather than by a dipping process with a spray mist system.
- the component 10 is rotated, for example, on a turntable 19.
- One or more spray nozzles 21 generate a mist of the liquid component to activate the polymerization of the surface layer.
- Polymerization system can be used with multiple independent initiator systems.
- One embodiment is a grain coated with ethylbarbituric acid which contains BPO inside.
- ethylbarbituric acid which contains BPO inside.
- a photoinitiator can serve as a second initiation system.
- a photoinitiator of the type diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO) is preferred.
- TPO diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
- UV radiation radicals for the polymerization. All radiation types from UVA, UVB to UVC can be used. UVA radiation is preferred for curing.
- the component 10 is immersed in a bath 12 with the liquid components 11.
- this bath are all the components that form a reactive and polymerizable mixture with the component in the component 10.
- the essential requirement of the mixture is that the components in the bath do not react or solidify very slowly without the component in the component.
- an infiltration mixture of 79% HEMA, 20% EGDMA, 0.5% DMPT, 0.5% TPO is particularly preferred.
- the device for immersion infiltration includes a bath 12, a liquid-permeable holder 16 for immersion and a hold-down device 17, 18 which prevents the component from floating in the immersion bath (see FIGS. 4 and 5).
- the immersion bath consists of a chemically resistant container 12. Preference is given to stainless steel. Depending on the infiltration medium, it can be heated to lower the viscosity of the infiltrate.
- a closure 14 protects the bath from contamination and entry of radiation which can lead to undesired polymerization.
- An extension represents a cooling device 13, which allows a particularly good preservation of the infiltration fluid.
- Preferred for the liquid-permeable holder 16 is a basket made of wire. On this is for holding down the component brackets 17 or a weight 18. An axis for lowering 15 allows an automatable and uniform dipping of the components.
- FIG. 6 shows the hardening of the surface layer with UV radiation 20.
- the choice of the process parameters therefore takes place in such a way that only a very thin layer is solidified in the edge region. This avoids distortion due to strong residual stresses.
- the monomer mixture contains 0.5% by weight TPO.
- the exposure takes place with UVA radiant tubes with an input power of 75 W at a distance of 10 cm.
- the component is moved in the radiation field.
- the movement allows the entry of UV radiation to otherwise shadowed areas.
- the movement can be done by rotation around all spatial axes. A rotational movement about only one axis is preferred.
- a turntable 19 with one or more degrees of freedom is preferred.
- the component is held in a holder made of wires, which have the smallest possible cross-section.
- a simple design represents a rust, which is connected to a rotation axis.
- a special device can be provided. By movement while the support points of the component 10 are changed in a time sequence.
- a simple embodiment illustrated in FIG. 7 illustrates two grate grates 22, 23, which are installed inside one another. A rust is shifted against the second in its height. As a result, the component is taken over by the higher grate and the contact points change 24,25.
Description
Claims
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DE102007049058A DE102007049058A1 (de) | 2007-10-11 | 2007-10-11 | Materialsystem und Verfahren zum Verändern von Eigenschaften eines Kunststoffbauteils |
PCT/DE2008/001593 WO2009046696A2 (de) | 2007-10-11 | 2008-10-01 | Materialsystem und verfahren zum verändern von eigenschaften eines kunststoffbauteiles |
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EP2200813A2 true EP2200813A2 (de) | 2010-06-30 |
EP2200813B1 EP2200813B1 (de) | 2011-03-23 |
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EP08801346A Active EP2200813B1 (de) | 2007-10-11 | 2008-10-01 | Verfahren zum steigern von festigkeit eines porösen kunststoffbauteiles |
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US (3) | US8349233B2 (de) |
EP (1) | EP2200813B1 (de) |
AT (1) | ATE502760T1 (de) |
DE (2) | DE102007049058A1 (de) |
ES (1) | ES2363113T3 (de) |
WO (1) | WO2009046696A2 (de) |
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-
2007
- 2007-10-11 DE DE102007049058A patent/DE102007049058A1/de not_active Ceased
-
2008
- 2008-10-01 AT AT08801346T patent/ATE502760T1/de active
- 2008-10-01 ES ES08801346T patent/ES2363113T3/es active Active
- 2008-10-01 WO PCT/DE2008/001593 patent/WO2009046696A2/de active Application Filing
- 2008-10-01 DE DE502008002970T patent/DE502008002970D1/de active Active
- 2008-10-01 EP EP08801346A patent/EP2200813B1/de active Active
- 2008-10-01 US US12/681,194 patent/US8349233B2/en not_active Expired - Fee Related
-
2012
- 2012-12-06 US US13/706,756 patent/US20130092082A1/en not_active Abandoned
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2015
- 2015-03-23 US US14/665,474 patent/US20150210822A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO2009046696A3 * |
Also Published As
Publication number | Publication date |
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ES2363113T3 (es) | 2011-07-20 |
WO2009046696A2 (de) | 2009-04-16 |
DE502008002970D1 (de) | 2011-05-05 |
WO2009046696A3 (de) | 2009-12-23 |
US20150210822A1 (en) | 2015-07-30 |
US20130092082A1 (en) | 2013-04-18 |
EP2200813B1 (de) | 2011-03-23 |
US20100244301A1 (en) | 2010-09-30 |
US8349233B2 (en) | 2013-01-08 |
DE102007049058A1 (de) | 2009-04-16 |
ATE502760T1 (de) | 2011-04-15 |
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